TWI672842B - Lithium ion secondary battery and method of producing the same - Google Patents
Lithium ion secondary battery and method of producing the same Download PDFInfo
- Publication number
- TWI672842B TWI672842B TW107113283A TW107113283A TWI672842B TW I672842 B TWI672842 B TW I672842B TW 107113283 A TW107113283 A TW 107113283A TW 107113283 A TW107113283 A TW 107113283A TW I672842 B TWI672842 B TW I672842B
- Authority
- TW
- Taiwan
- Prior art keywords
- positive electrode
- electrode mixture
- lithium
- mixture layer
- negative electrode
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 70
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 69
- 239000000203 mixture Substances 0.000 claims abstract description 127
- 239000007774 positive electrode material Substances 0.000 claims abstract description 43
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 24
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 15
- 230000000996 additive effect Effects 0.000 claims abstract description 10
- 239000011572 manganese Substances 0.000 claims description 49
- 238000007600 charging Methods 0.000 claims description 34
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 15
- 229910013716 LiNi Inorganic materials 0.000 claims description 13
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims description 13
- 239000007773 negative electrode material Substances 0.000 claims description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims description 10
- 159000000002 lithium salts Chemical class 0.000 claims description 10
- 238000000619 electron energy-loss spectrum Methods 0.000 claims description 7
- 229910018584 Mn 2-x O 4 Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 6
- 238000005430 electron energy loss spectroscopy Methods 0.000 claims description 6
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052789 astatine Inorganic materials 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 238000001035 drying Methods 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 10
- -1 hydrogen ions Chemical class 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 239000011149 active material Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
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- 239000002482 conductive additive Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 4
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
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- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical class COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
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- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- GBPVMEKUJUKTBA-UHFFFAOYSA-N methyl 2,2,2-trifluoroethyl carbonate Chemical compound COC(=O)OCC(F)(F)F GBPVMEKUJUKTBA-UHFFFAOYSA-N 0.000 description 2
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000000992 sputter etching Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- 241000252073 Anguilliformes Species 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical class OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
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- 238000007605 air drying Methods 0.000 description 1
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- 230000001174 ascending effect Effects 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
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- 239000002800 charge carrier Substances 0.000 description 1
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- 239000013626 chemical specie Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000012257 stirred material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 230000026676 system process Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- MVGWWCXDTHXKTR-UHFFFAOYSA-J tetralithium;phosphonato phosphate Chemical compound [Li+].[Li+].[Li+].[Li+].[O-]P([O-])(=O)OP([O-])([O-])=O MVGWWCXDTHXKTR-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/049—Processes for forming or storing electrodes in the battery container
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/044—Activating, forming or electrochemical attack of the supporting material
- H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
- H01M4/0447—Forming after manufacture of the electrode, e.g. first charge, cycling of complete cells or cells stacks
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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Abstract
本案提出一種製造鋰離子二次電池的方法。使用包括含括鋰錳複合氧化物之正極活性材料、水性溶劑、且另外包括作為添加劑的Li5 FeO4 之水性正極混合物糊,正極混合物層形成於正極電流收集器上。This case proposes a method for manufacturing a lithium ion secondary battery. The positive electrode mixture layer was formed on a positive electrode current collector using an aqueous positive electrode mixture paste including a positive electrode active material containing a lithium manganese composite oxide, an aqueous solvent, and additionally including Li 5 FeO 4 as an additive.
Description
[0001]本發明係關於鋰離子二次電池及其製造方法,且特定言之,係關於包括水性溶劑之正極混合物糊、使用彼製造鋰離子二次電池之方法、及使用該製造方法可製造的鋰離子二次電池。[0001] The present invention relates to a lithium ion secondary battery and a method for manufacturing the same, and more particularly, to a positive electrode mixture paste including an aqueous solvent, a method for manufacturing a lithium ion secondary battery using the same, and a method capable of manufacturing the same Lithium-ion secondary battery.
[0002]由於鋰離子二次電池質輕且可得到高能量密度,所以它們較佳地用於供驅動載具(如,電動載具和混合動力載具)使用的高輸出功率供應器。近年來,已開發比相關技術中者具有更高電位的正極活性材料且預期對於作為用於驅動載具的電源供應器之鋰離子二次電池的需求會逐漸提高。此類型的正極活性材料的例子包括含有元素錳的尖晶石結構正極活性材料。例如,已經知道尖晶石結構鋰和錳複合氧化物(LiMn2 O4 )中的一些錳經鎳取代之尖晶石結構鋰鎳錳複合氧化物(LiNix Mn2-x O4 ),例如,LiNi0.5 Mn1.5 O4 ,為有利的高電位型正極活性材料,其中基於金屬鋰,其正極操作電位的上限電位是4.5V或更高。 [0003]附帶地,隨著組成物以糊或漿形式製得(下文中稱為“正極混合物糊”),使用非水性溶劑(即,有機溶劑)製備的非水性正極混合物糊,以使用以上的正極活性材料在正極電流收集器上形成正極混合物層(亦稱為正極活性材料層)已經常被用於相關技術中。但是,為了要減少處理非水性溶劑所花的時間和功夫及成本、減少環境負擔等,較佳地使用以水性溶劑(即,主要含有H2 O的溶劑,基本上,水)製備的水性正極混合物糊。[0002] Since lithium-ion secondary batteries are lightweight and can obtain high energy density, they are preferably used for high-output power supplies for driving vehicles such as electric vehicles and hybrid vehicles. In recent years, a positive active material having a higher potential than those in the related art has been developed and it is expected that the demand for a lithium ion secondary battery as a power supply for driving a vehicle will gradually increase. Examples of this type of positive electrode active material include a spinel structure positive electrode active material containing elemental manganese. For example, some spinel-structured lithium and manganese composite oxides (LiMn 2 O 4 ) are known as spinel-structured lithium-nickel-manganese composite oxides (LiNi x Mn 2-x O 4 ), such as LiNi 0.5 Mn 1.5 O 4 is an advantageous high-potential type positive electrode active material in which the upper limit potential of the positive electrode operating potential is 4.5 V or higher based on metallic lithium. [0003] Incidentally, as the composition is prepared in the form of a paste or slurry (hereinafter referred to as a "positive electrode mixture paste"), a non-aqueous positive electrode mixture paste prepared using a non-aqueous solvent (ie, an organic solvent) to use the above A positive electrode active material on a positive current collector to form a positive electrode mixture layer (also referred to as a positive electrode active material layer) has been often used in related technologies. However, in order to reduce the time and effort and cost of processing non-aqueous solvents, reduce environmental burden, etc., it is preferable to use an aqueous positive electrode prepared with an aqueous solvent (that is, a solvent mainly containing H 2 O, basically water). The mixture is pasty.
[0004]但是,使用水性正極混合物糊時,不同於非水性正極混合物糊,會發生因為水性溶劑的存在而發生問題。例如,所使用的正極活性材料包括至少含有鋰和錳作為金屬元素的鋰錳複合氧化物時,若水與鋰錳複合氧化物製的正極活性材料粒子接觸,則會發生水中的氫離子和正極活性材料中的鋰離子的交換反應,糊(漿)的pH提高,大量的氫離子黏著至活性材料粒子表面。因此,當曝於高溫時,例如,藉由將正極混合物糊施於正極電流收集器而形成的正極混合物層於高溫乾燥時,或者在電池組裝之後於高溫進行老化處理時,氧與在活性材料表面上的氫離子一起脫附而活性材料被帶到缺氧狀態。則,活性材料中含有的Mn的價數會因為電荷補償而自4+降至3+。因為此價數的降低會引發電池的內部電阻提高,所以非較佳者。特別地,在正極活性材料粒子的表面上形成Mn3+ 厚層(例如,最大厚度達100 nm的Mn3+ 厚層)時,由於內部電阻提高,其會與非水性電解質液接觸,此非所欲者。 [0005]關於以上者,例如,日本未審查專利申請公開第2016-122550號(JP 2016-122550 A),揭示的一種技術中,當製備用於製備水性正極的糊時,包括磷酸單酯和磷酸二酯中之至少一者的分散劑混入其中,鋰錳複合氧化物製造的正極活性材料粒子的周圍被磷酸酯分子所環繞,因此防止氧脫附和Mn自正極活性材料外流。在 JP 2016-122550 A中所描述的技術中,隨著防止氧自正極活性材料脫附之技術,可得到某些結果。但是,此並非氧(基本上,離子形式,如氧化物離子和過氧化物離子)自周圍供應至正極活性材料且Mn的價數自3+正向地提高至4+之技術。 [0006]因此,在本發明中,即使使用水性正極混合物糊,在正極電流收集器上形成包括鋰錳複合氧化物之正極活性材料的正極混合物層,其具有有效地供應氧及提高Mn的價數(自3+恢復成4+)的可能性。 [0007]本發明提出一種用以形成鋰離子二次電池的正極混合物層之水性正極混合物糊。此處所提出的水性正極混合物包括含括鋰錳複合氧化物之正極活性材料和水性溶劑,且另外包括作為添加劑的Li5 FeO4 。作為本發明的第一特點,提出一種製造鋰離子二次電池之方法。即,此處所揭示之製造鋰離子二次電池之方法係製造包括正極混合物層在正極電流收集器上的正極、包括負極混合物層在負極電流收集器上的負極、和含有鋰鹽的非水性電解質液之鋰離子二次電池之方法。該負極混合物層包括負極活性材料。該方法包括製備包括含括鋰錳複合氧化物之正極活性材料、水性溶劑、和另包括作為添加劑的Li5 FeO4 之水性正極混合物糊;藉由使用該水性正極混合物糊,在正極電流收集器上形成正極混合物層以製備正極;使用正極和負極製備電極體,藉由將該電極體和非水性電解質液納入電池殼中,構成電池組裝品;及在該電池組裝品上進行初步充電程序。 [0008]此外,作為第二特點,本案提出一種鋰離子二次電池組裝品。該鋰離子二次電池組裝品包括電極體,其包括含括正極混合物層在正極電流收集器上的正極、和含括負極混合物層在負極電流收集器上的負極,和包括鋰鹽之非水性電解質液,其中該正極混合物層包括作為正極活性材料的鋰錳複合氧化物並包括作為添加劑的Li5 FeO4 。該負極混合物層包括負極活性材料。此處的用語“鋰離子二次電池組裝品”是指在進行初步充電程序之前,構成鋰離子二次電池的組件和材料在一個步驟中以電池體形式組裝的構造(即,組裝品)。在鋰離子二次電池組裝品上進行初步充電程序(亦稱為調節處理)時,其可作為鋰離子二次電池。 [0009]在製造本案揭示的鋰離子二次電池和鋰離子二次電池組裝品的方法中,具有以上組成的水性正極混合物糊用以形成正極混合物層。本發明者發現,當Li5 FeO4 與包括鋰錳複合氧化物(下文中簡稱為“含錳的正極活性材料”)的正極活性材料一起混入正極混合物層中時,在初步充電程序的期間內,Li5 FeO4 在正極混合物層中以下式所示反應:2Li5 FeO4 =5Li2 O+Fe2 O3 ,且此外,在初步充電之後進行高溫老化的期間內,自Li2 O(其為反應產物)生成氧並供應至含錳的正極活性材料。因此,在使用此處揭示的製造鋰離子二次電池的方法製得的鋰離子二次電池(及鋰離子二次電池組裝品)中,在初步充電程序(調節處理)的步驟中,自Li5 FeO4 衍生的氧(基本上,離子形式,如,氧化物離子)供應至含錳的正極活性材料,Mn3+ 的量會降低並促進Mn4+ 的再生。因此,能夠防止電池的內部電阻(反應電阻)因為Mn3+ 的生成和累積而提高,防止電池性能受損,和,例如,防止充電和放電特性受損。此處,在日本未審查專利申請公開第2015-88268號(JP 2015-88268 A)、日本未審查專利申請公開第2014-157653號( JP 2014-157653 A)、和日本未審查專利申請公開第 2014-67629號(JP 2014-67629 A)中,描述含有Li5 FeO4 的鋰離子二次電池。但是,在本發明中,使用目的、應用、和與Li5 FeO4 的活性材料之合併不同,且在技術構思方面沒有共同點。 [0010]此外,較佳地,在製造根據第一特點的鋰離子二次電池及根據第二特點的鋰離子二次電池組裝品之方法中,以正極混合物糊中之100重量%的固體總含量或構成正極混合物層的100重量%的固體總含量計,Li5 FeO4 的添加量可以在0.3重量%至2.0重量%的範圍內。在所含有之Li5 FeO4 相對於構成正極混合物層的固體總含量之比例在此範圍內的正極混合物層中,在初步充電程序期間內,適當量的氧(基本上,離子形式)可施用於含錳的正極活性材料。此外,由於Li5 FeO4 的含量未過量,所以可防止正極電流收集器的pH因為有過量的Li5 FeO4 的分解產物存在而提高且能夠改良電池的耐久性。 [0011]在製造根據第一特點的鋰離子二次電池及根據第二特點的鋰離子二次電池組裝品之方法中,可以含括LiNi0.5 Mn1.5 O4 作為含錳的正極活性材料。當5 V-等級之含錳的正極活性材料與添加劑:Li5 FeO4 一起使用時,可提供高電位和高容量鋰離子二次電池。 [0012]第一特點中,可以含括LiNi0.5 Mn1.5 O4 、 LiMn2 O4 、LiNix Mn2-x O4 、LiNix Mey Mn2-x-y O4 、Li2 MnO3 、和LiMnPO4 中之至少一者作為正極活性材料。 LiNix Mn2-x O4 中的x可符合0<x<2,而 LiNix Mey Mn2-x-y O4 中的Me可為選自包括Fe、Ti、Al、Si、Mg、Ca、Ba、Sr、Sc、V、Cr、Co、Cu、Zn、Ga、Y、Ru、Rh、Pd、In、Sn、Sb、La、Ce、Sm、Zr、Nb、Ta、Mo、和 W之群組中之至少一種元素。LiNix Mey Mn2-x-y O4 中的x和y可符合0<(x+y)<2。 [0013]第一特點可以另包括在該電池組裝品初步充電之後,進行老化處理,其中該電池組裝品維持於35℃或更高的溫度,達高於或等於6小時且低於或等於50小時的時間。 [0014]此外,作為第三特點,提出一種鋰離子二次電池,其包括:電極體,其包括含括正極混合物層在正極電流收集器上的正極、和含括負極混合物層在負極電流收集器上的負極;和含有鋰鹽之非水性電解質液。然後,在此處揭示的鋰離子二次電池中,正極混合物層包括鋰錳複合氧化物作為正極活性材料。負極混合物層包括負極活性材料。在初步充電程序之後的一個步驟中,使用STEM-EELS方法,在正極混合物層的截面(即,藉Ar離子研磨所得之經CP處理的截面)中,藉由進行自表面進入正極活性材料粒子中的線分析得到EELS光譜,在線分析的EELS光譜中,介於在粒子表面上的錳(Mn)最大峰位置處的O峰高度(A)和在O最大峰位置處的O峰高度(B)之間的O峰高度比(A/B)的平均值為0.8或更高。 [0015]以上定義之“基於STEM-EELS方法的O峰比(A/B)”可為在初步充電程序之後,鋰離子二次電池的正極混合物層中的氧供應狀態的指標。因此,在此處揭示的鋰離子二次電池中,O峰比的平均值是0.8或更高,或更佳地為0.9或更高。此指出在初步充電程序之後,足量的氧(離子形式)供應至正極混合物層中所含之含錳的正極活性材料,例如,LiNi0.5 Mn1.5 O4 。因此,在此處揭示的鋰離子二次電池中,例如,在初步充電程序之後,Mn3+ 更容易回到Mn4+ 。因此,根據此處揭示的鋰離子二次電池能夠防止電池的內部電阻(反應電阻)因為Mn3+ 的生成和累積而提高,防止電池性能受損,和,例如,防止充電和放電特性受損。[0004] However, when an aqueous positive electrode mixture paste is used, unlike non-aqueous positive electrode mixture pastes, problems occur due to the presence of an aqueous solvent. For example, when the positive electrode active material used includes a lithium-manganese composite oxide containing at least lithium and manganese as metal elements, if water contacts the positive electrode active material particles made of the lithium-manganese composite oxide, hydrogen ions in the water and positive electrode activity occur. The exchange reaction of lithium ions in the material increases the pH of the paste (slurry), and a large amount of hydrogen ions adhere to the surface of the active material particles. Therefore, when exposed to high temperature, for example, when a positive electrode mixture layer formed by applying a positive electrode mixture paste to a positive current collector is dried at a high temperature, or when an aging treatment is performed at a high temperature after battery assembly, oxygen and the active material The hydrogen ions on the surface are desorbed together and the active material is brought to an anoxic state. Then, the valence of Mn contained in the active material will decrease from 4+ to 3+ due to charge compensation. Because this decrease in valence will cause the internal resistance of the battery to increase, it is not preferred. In particular, when Mn 3+ form a thick layer (e.g., a maximum thickness of 100 nm thick layer of Mn 3+) on the surface of the positive electrode active material particles, since the increase in internal resistance, which will contact with the non-aqueous electrolyte solution, this non- The desire. [0005] Regarding the above, for example, Japanese Unexamined Patent Application Publication No. 2016-122550 (JP 2016-122550 A), in a technique disclosed, when preparing a paste for preparing an aqueous positive electrode, a phosphate monoester and A dispersant of at least one of the phosphoric diesters is mixed therein, and the periphery of the positive electrode active material particles made of the lithium manganese composite oxide is surrounded by the phosphate molecule, thereby preventing oxygen desorption and Mn from flowing out of the positive electrode active material. Among the techniques described in JP 2016-122550 A, with the technique of preventing the desorption of oxygen from the positive electrode active material, some results can be obtained. However, this is not a technique in which oxygen (basically, ionic forms such as oxide ions and peroxide ions) is supplied from the surroundings to the positive electrode active material and the valence of Mn is positively increased from 3+ to 4+. [0006] Therefore, in the present invention, even if an aqueous positive electrode mixture paste is used, a positive electrode mixture layer including a positive electrode active material of a lithium manganese composite oxide is formed on a positive electrode current collector, which has an effect of efficiently supplying oxygen and increasing the price of Mn. Number (from 3+ to 4+). [0007] The present invention provides an aqueous positive electrode mixture paste for forming a positive electrode mixture layer of a lithium ion secondary battery. The aqueous positive electrode mixture proposed here includes a positive electrode active material including a lithium manganese composite oxide and an aqueous solvent, and additionally includes Li 5 FeO 4 as an additive. As a first feature of the present invention, a method for manufacturing a lithium ion secondary battery is proposed. That is, the method for manufacturing a lithium ion secondary battery disclosed herein is to manufacture a positive electrode including a positive electrode mixture layer on a positive current collector, a negative electrode including a negative electrode mixture layer on a negative current collector, and a non-aqueous electrolyte containing a lithium salt. Method for liquid lithium ion secondary battery. The negative electrode mixture layer includes a negative electrode active material. The method includes preparing an aqueous positive electrode mixture paste including a positive electrode active material including a lithium manganese composite oxide, an aqueous solvent, and Li 5 FeO 4 as an additive; by using the aqueous positive electrode mixture paste, a positive current collector is used. A positive electrode mixture layer is formed thereon to prepare a positive electrode; an electrode body is prepared using the positive electrode and the negative electrode, and the electrode body and a non-aqueous electrolyte solution are incorporated into a battery case to constitute a battery assembly; and a preliminary charging procedure is performed on the battery assembly. [0008] In addition, as a second feature, the present application proposes a lithium ion secondary battery assembly. The lithium ion secondary battery assembly includes an electrode body including a positive electrode including a positive electrode mixture layer on a positive current collector, a negative electrode including a negative electrode mixture layer on a negative current collector, and a non-aqueous material including a lithium salt. An electrolyte solution, wherein the positive electrode mixture layer includes a lithium manganese composite oxide as a positive electrode active material and includes Li 5 FeO 4 as an additive. The negative electrode mixture layer includes a negative electrode active material. The term “lithium-ion secondary battery assembly” herein refers to a structure (ie, an assembly) in which components and materials constituting the lithium-ion secondary battery are assembled in one step before the preliminary charging process is performed. It can be used as a lithium-ion secondary battery when a preliminary charging procedure (also referred to as conditioning treatment) is performed on the lithium-ion secondary battery assembly. [0009] In the method for manufacturing a lithium ion secondary battery and a lithium ion secondary battery assembly disclosed in this application, the aqueous positive electrode mixture paste having the above composition is used to form a positive electrode mixture layer. The inventors have discovered that when Li 5 FeO 4 is mixed into a positive electrode mixture layer together with a positive electrode active material including a lithium manganese composite oxide (hereinafter referred to as “manganese-containing positive electrode active material”), during the period of the preliminary charging procedure Li 5 FeO 4 reacts in the positive electrode mixture layer with the following formula: 2Li 5 FeO 4 = 5Li 2 O + Fe 2 O 3 , and in addition, during the period of high temperature aging after preliminary charging, from Li 2 O (which As a reaction product), oxygen is generated and supplied to a positive electrode active material containing manganese. Therefore, in a lithium-ion secondary battery (and a lithium-ion secondary battery assembly) produced using the method of manufacturing a lithium-ion secondary battery disclosed herein, in a step of a preliminary charging procedure (adjustment process), 5 FeO 4 -derived oxygen (basically, ionic forms, such as oxide ions) is supplied to the manganese-containing positive electrode active material, and the amount of Mn 3+ decreases and promotes regeneration of Mn 4+ . Therefore, it is possible to prevent the internal resistance (reaction resistance) of the battery from being increased due to the generation and accumulation of Mn 3+ , prevent the battery performance from being impaired, and, for example, prevent the charging and discharging characteristics from being impaired. Here, in Japanese Unexamined Patent Application Publication No. 2015-88268 (JP 2015-88268 A), Japanese Unexamined Patent Application Publication No. 2014-157653 (JP 2014-157653 A), and Japanese Unexamined Patent Application Publication No. In 2014-67629 (JP 2014-67629 A), a lithium ion secondary battery containing Li 5 FeO 4 is described. However, in the present invention, the purpose of use, application, and integration with Li 5 FeO 4 active materials are different, and there is no common point in terms of technical ideas. [0010] Furthermore, preferably, in a method of manufacturing a lithium ion secondary battery according to the first feature and a lithium ion secondary battery assembly according to the second feature, 100% by weight of the total solids in the positive electrode mixture paste is used. The content of Li 5 FeO 4 may be in the range of 0.3% to 2.0% by weight based on the content or the total solid content of 100% by weight constituting the positive electrode mixture layer. In a positive electrode mixture layer containing Li 5 FeO 4 with respect to the total solid content constituting the positive electrode mixture layer within this range, an appropriate amount of oxygen (basically, an ionic form) may be applied during the preliminary charging procedure For manganese-containing positive active materials. In addition, since the content of Li 5 FeO 4 is not excessive, it is possible to prevent the pH of the positive electrode current collector from being increased due to the presence of excessive decomposition products of Li 5 FeO 4 and to improve battery durability. [0011] In a method of manufacturing a lithium ion secondary battery according to the first feature and a lithium ion secondary battery assembly according to the second feature, LiNi 0.5 Mn 1.5 O 4 may be included as a manganese-containing positive electrode active material. When a 5 V-grade manganese-containing positive active material is used with an additive: Li 5 FeO 4 , a high-potential and high-capacity lithium ion secondary battery can be provided. [0012] The first feature may include LiNi 0.5 Mn 1.5 O 4 , LiMn 2 O 4 , LiNi x Mn 2-x O 4 , LiNi x Me y Mn 2-xy O 4 , Li 2 MnO 3 , and LiMnPO At least one of 4 is used as a positive electrode active material. X in LiNi x Mn 2-x O 4 may satisfy 0 <x <2, and Me in LiNi x Me y Mn 2-xy O 4 may be selected from the group consisting of Fe, Ti, Al, Si, Mg, Ca, Ba, Sr, Sc, V, Cr, Co, Cu, Zn, Ga, Y, Ru, Rh, Pd, In, Sn, Sb, La, Ce, Sm, Zr, Nb, Ta, Mo, and W At least one element in the group. X and y in LiNi x Me y Mn 2-xy O 4 may satisfy 0 <(x + y) <2. [0013] The first feature may further include performing an aging treatment after the battery assembly is initially charged, wherein the battery assembly is maintained at a temperature of 35 ° C or higher for 6 hours or more and 50 or less Hours of time. [0014] In addition, as a third feature, a lithium-ion secondary battery is proposed, which includes an electrode body including a positive electrode including a positive electrode mixture layer on a positive current collector, and a negative electrode current collecting layer including a negative electrode mixture layer. The negative electrode on the device; and a non-aqueous electrolyte solution containing a lithium salt. Then, in the lithium ion secondary battery disclosed herein, the positive electrode mixture layer includes a lithium manganese composite oxide as a positive electrode active material. The negative electrode mixture layer includes a negative electrode active material. In a step after the preliminary charging procedure, the STEM-EELS method is used to cross-section the positive electrode mixture layer (that is, the CP-treated section obtained by Ar ion milling) from the surface into the positive electrode active material particles. The EELS spectrum is obtained by line analysis. In the EELS spectrum analyzed online, the O peak height (A) at the position of the largest peak of manganese (Mn) on the particle surface and the O peak height (B) at the position of the O maximum peak. The average value of the O peak height ratio (A / B) between them is 0.8 or higher. [0015] The "O-peak ratio (A / B) based on the STEM-EELS method" defined above may be an indicator of the oxygen supply state in the positive electrode mixture layer of the lithium ion secondary battery after the preliminary charging procedure. Therefore, in the lithium ion secondary battery disclosed herein, the average value of the O peak ratio is 0.8 or higher, or more preferably 0.9 or higher. This indicates that after the preliminary charging procedure, a sufficient amount of oxygen (ionic form) is supplied to the manganese-containing positive active material contained in the positive electrode mixture layer, for example, LiNi 0.5 Mn 1.5 O 4 . Therefore, in the lithium-ion secondary battery disclosed here, for example, Mn 3+ is more easily returned to Mn 4+ after the preliminary charging procedure. Therefore, according to the lithium ion secondary battery disclosed herein, it is possible to prevent the internal resistance (reaction resistance) of the battery from being increased due to the generation and accumulation of Mn 3+ , prevent the battery performance from being impaired, and, for example, prevent the charging and discharging characteristics from being impaired. .
[0017]以下將參照附圖,詳細描述此處所揭示之水性正極混合物糊、使用該水性正極混合物糊製造鋰離子二次電池之方法、及藉該製造方法得到之鋰離子二次電池(及在初步充電程序之前的電池組裝品)之例示具體實施例。本說明書中特別提及之用於實施的必要組件以外的組件可以被嫻於此技術之人士視為是基於本領域相關技術的設計事項。本發明可以基於此說明書中所揭示的內容和此領域之共同的一般技術知識實施。此處,此說明書中,當數值範圍以A至B描述時(此處,A和B是任意數字)時,與一般闡釋為A或更高且B或更低者相同。 [0018]此說明書中,用語“鋰離子二次電池”是指非水性電解液中的鋰離子用於電荷轉移之二次電池。此外,用語“電極體”是指形成包括正極、負極、和可作為介於正和負極之間的隔離物之多孔絕緣層之電池主體的結構。用語“正極活性材料”或“負極活性材料”是指能夠可逆地阻擋和釋出作為電荷載體的化學物種(鋰離子二次電池中的鋰離子)之化合物。 [0019]如圖1中所示者,根據本具體實施例之鋰離子二次電池100是電極體20(基本上,扁平的電極體20)和非水性電解質液(未示)納入電池殼(即,外部容器)30中的電池。該電池殼30包括一端具有開口的盒形(即,具有底部的平行六面體)殼主體32和用以封住殼主體32的蓋34。即,當電池經一般放置或使用時,此一端對應於較上端。作為電池殼30的材料,可以較佳地使用具有有利的導熱性之輕質金屬材料,例如,鋁、不銹鋼、或鍍鎳的鋼。此外,用於外部連接的正極端42和負極端44配置於蓋34中。此外,在蓋34中,配置排氣閥36(其經設定以於電池殼30的內部壓力提高至預定程度或更高時用以釋放內部壓力)、和入口(未示)(非水性電解質液經由此入口注入電池殼30中)。此處,在電池殼30中,蓋34焊接至電池殼主體32的開口周圍,並因此而可結合(密封)介於電池殼主體32和蓋34之間的邊界。 [0020]如圖2中所示者,根據本具體實施例之電極體20是捲繞的電極體20,其中,拉長的正極50、拉長的負極60、和拉長的隔離物70層疊並於縱向捲繞。本具體實施例中,在捲繞的電極體20中,具有支路指向的捲繞軸以捲繞軸具有支路指向的狀態納入電池殼30中,即,蓋34自彼安裝於垂直於捲繞的電極體20的捲繞軸的方向(電池殼30上方)。特定言之,根據本具體實施例之捲繞的電極體20係藉由將正極(正極片)50(其中,正極混合物層54於縱向形成於由鋁箔之類形成之拉長的正極電流收集器52的一表面或二表面(此處,二表面)上)和負極(負極片)60(其中,負極混合物層64於縱向形成於由銅箔之類形成之拉長的負極電流收集器62的一表面或二表面(此處,二表面)上)與介於其間之拉長的隔離物(隔離片)70疊置並在縱向以扁平形狀捲繞。在捲繞的電極體20之捲繞軸方向的中央部分,形成正極混合物層54、負極混合物層64、和隔離物70緊密層疊之捲繞的核心部分。此外,正極電流收集板和負極電流收集板(未示)結合至未形成配件52a的正極活性材料且未形成配件62a的負極混合物層(其自捲繞軸方向捲繞的電極體20的兩端突出)以形成電池的電流收集構造。但是,由於此構造類似於包括相關技術之捲繞的電極體之矩形鋰離子二次電池,所以將不描述其細節。此處,實施本發明時,電極體的類型不須限制於所示的捲繞類型。例如,可以使用包括藉由將複數個正極片和負極片與介於其間的隔離物層疊而形成之層疊型電極體之鋰離子二次電池。此外,如由此說明書中揭示的技術資訊可清楚瞭解者,電池的形狀不限於以上的矩形。 [0021]如圖3中所示者,根據本具體實施例之製造方法包括正極混合物糊製程(S10)(其中,製備具有以下描述之組成的水性正極混合物糊)、正極製程(S20)(其中,製得的正極混合物糊施用至正極電流收集器以製備正極)、電極體製程(S30)(其中,使用製得的正極和另外製得的負極製得電極體)、電池組裝品建構程序(S40)(其中,製得的電極體和非水性電解質液納入預定的電池殼以建構電池組裝品)、及初步充電程序(S50)(其中,建構的電池組裝品經初步充電以得到可使用的鋰離子二次電池)。以下將詳細描述該等程序。 [0022]首先,將描述正極混合物糊製程(S10)。所用的水性正極混合物糊係以包括含錳的正極活性材料和水性溶劑、及額外包括Li5
FeO4
作為添加劑而製得。作為所用之含錳的正極活性材料,可以使用相關技術之鋰離子二次電池中使用之各式各樣含錳的正極活性材料。較佳地,可以使用各式各樣的高電位型鋰錳複合氧化物(基於金屬鋰,其正極操作電位的上限電位是4.3 V或更高)。可以適當地使用基於金屬鋰,正極操作電位的上限電位為4.5 V或更高,且特別地,接近5.0 V,的高電位型鋰錳複合氧化物,其通常被稱為5 V-等級氧化物。例如,尖晶石結構鋰和錳複合氧化物(LiMn2
O4
)、尖晶石結構鋰錳鎳複合氧化物(其中,一些錳經鎳取代(LiNix
Mn2-x
O4
,此處,0<x<2,較佳地,0<x<1)、和含有其他金屬元素之含鋰、含錳和含鎳的複合氧化物(LiNix
Mey
Mn2-x-y
O4
,此處Me是選自包括Fe、Ti、Al、Si、Mg、Ca、Ba、Sr、Sc、V、Cr、Co、Cu、Zn、Ga、Y、Ru、Rh、Pd、In、Sn、Sb、La、Ce、Sm、Zr、Nb、Ta、Mo、和 W (更佳地,至少一種過渡金屬元素,如,Co、Ti、Fe、或 W)之群組中之一、二或更多種元素,0<(x+y)<2,更佳地,0<(x+y)<1)等可為例示。或者,可以使用成層結構或橄欖石結構鋰錳複合氧化物(例如,Li2
MnO3
和LiMnPO4
)。其中,特別佳地使用高電位尖晶石結構鋰錳複合氧化物,例如,LiNi0.5
Mn1.5
O4
(基於金屬鋰,其正極操作電位的上限電位為4.5 V或更高)。 [0023]此處所揭示之正極混合物糊是使用水性溶劑製備的水性正極混合物糊。水性溶劑的例子包括自來水、去離子水、和蒸餾水。較佳地使用去離子水或蒸餾水,此因幾乎沒有雜質含於其中之故。此外,此處所揭示之水性正極混合物糊包括 Li5
FeO4
作為添加劑。雖未特別限制,以製得的正極混合物糊中之固體總含量(100重量%)計,Li5
FeO4
的添加量較佳地為0.3重量%或更高且2.0重量%或更低,且更佳為0.6重量%或更高且1.5重量%或更低。例如,基本上,約0.3 g至2 g的Li5
FeO4
以粉末形式添加至 100 g不含有Li5
FeO4
的固體糊中。以此含量(組成比),在初步充電期間內,將適當的氧(基本上,離子形式)量供應至含錳的正極活性材料,可防止Mn3+
量的提高且可促進Mn4+
安定地存在。此外,由於Li5
FeO4
的含量未過量,所以可防止正極電流收集器因為Li5
FeO4
的分解產物存在造成pH提高而腐蝕,且亦可適當地維持耐久性。 [0024]此外,除了以上的正極活性材料、複合材料粉末、和水性溶劑以外,此處所揭示之水性正極混合物糊可以無特別限制地包括相關技術中之此類型的糊材料中所含括之各式各樣的材料作為組份。例如,為了要改良在正極混合物層中的導電性,導電性添加劑,如,碳黑(例如,乙炔黑)、石墨粒子、或碳奈米管,較佳地以10重量%或更低(例如,3重量%至10重量%)的比例添加,此以糊中的固體總含量設定為100重量%計。此外,作為黏合劑(黏合劑)、水溶性或水可分散的聚合物,如,氟樹脂(如,聚四氟乙烯(PTFE))、橡膠(如,苯乙烯丁二烯共聚物(SBR))、聚乙烯醇(PVA)、乙酸乙烯酯共聚物、聚丙烯酸(PAA)、或丙烯酸酯聚合物較佳地以5重量%或更低(例如,1重量%至5重量%)的比例添加,此以糊中的固體總含量設定為100重量%計。此外,作為稠化劑,以纖維素為基礎的聚合物,如,羧甲基纖維素(CMC)或羥丙基甲基纖維素(HPMC)較佳地以3重量%或更低(例如,0.5重量%至3重量%)的比例添加,此以糊中的固體總含量設定為100重量%計。此外,作為酸消耗劑,可以添加適當量(例如,0.1重量%至3重量%)的磷酸鋰、焦磷酸鋰之類。 [0025]雖未特別限制,例如,如圖4中所示的流程圖中,首先,以上各式各樣的組份、活性材料粒子、導電性添加劑、和Li5
FeO4
(粒子形式)使用滾磨機或另一適當的分散機混合以製備混合的粉末材料。之後,已有稠化劑事先分散(或溶解)於其中的水性溶劑(基本上,水,如,去離子水)添加至在適當的分散機中製得之混合的粉末材料中並充分分散。之後,添加黏合劑(黏合劑)並充分混於其中,可製備所欲的水性正極混合物糊。適當的固體含量比例是70重量%或更高(例如,70重量%至85重量%)。使用磷酸之類調整pH,且較佳地將該糊的pH調整在中性範圍內(例如,約7至11)。 [0026]之後,將描述正極製程(S20)。此程序中,作為製備的(製得的)正極混合物糊,水性正極混合物糊施用(塗覆)於正極電流收集器的表面(一表面或二表面),此使用適當的塗覆裝置(如,凹版塗佈機、縫隙塗佈機、模具塗佈機、間歇塗佈機、或浸泡塗佈機)進行。之後,藉由進行乾燥處理(如,空氣乾燥、加熱、或在已施用水性正極混合物糊的正極電流收集器上減壓)自經塗覆的產物移除水,並製備正極混合物層形成於正極電流收集器上的正極片。此乾燥處理沒有特別的限制,且可藉相關技術的一般方法(例如,熱乾燥或減壓乾燥)進行。例如,考慮產製效率,可以適當地使用熱乾燥。考慮在短時間內有效地乾燥,具有預定溫度的熱風送至用於乾燥的正極混合物層(塗覆產物)之熱風乾燥適用。乾燥溫度設定於構成正極混合物層的構成組份(基本上,正極活性材料、導電性添加劑、黏合劑等)不會改變的溫度。例如,乾燥溫度可設定於120℃至200℃。可以根據條件(如,用於熱風乾燥的乾燥溫度和空氣容量)適當地設定乾燥時間。通常,可使用10秒至300秒(基本上,20秒至200秒,例如,30秒至100秒)的乾燥時間。正極製程(S20)可以另包括對正極混合物層施壓的程序。必要時,進行適當的施壓加工之時,可調整正極混合物層的性質(例如,平均厚度、活性材料密度、和孔隙度)。 [0027]此處,無關於正極製程(S20),製備相對的負極。但是,負極這方本身的製程與相關技術的鋰離子二次電池的負極之製備相同。由於此程序未特徵化本發明,將不描述其細節。僅大綱描述如下。可以無特別限制地使用可作為鋰離子二次電池的負極活性材料之各式各樣的材料中之一、二或更多者作為建構負極混合物層的負極活性材料。較佳的例子包括至少一配件具有石墨結構(層狀結構)的碳材料,如,石墨、非可石墨化的碳(硬碳)、易石墨化的碳(軟碳)、和碳奈米管。為了要得到高能量密度,可以較佳地使用以石墨為基礎的材料,如,天然石墨(石墨)或人造石墨。除了負極活性材料以外,必要時,可作為一般鋰離子二次電池中的負極混合物層的構成組份的一、二或更多種材料可含括於負極混合物層中。此材料的例子包括黏合劑和各式各樣的添加劑。可以適當地使用聚合物材料(如,SBR或PTE)作為黏合劑。此外,可以適當地使用各式各樣的添加劑,如,稠化劑和分散劑。例如,可以適當地使用纖維素系聚合物(如,CMC)作為稠化劑。當藉由將負極活性材料和視所須而使用的以上材料分散於適當溶劑(例如,水性溶劑,如,蒸餾水)而以糊或漿製備的組成物(負極混合物糊)施用至負極電流收集器時,糊中所含括的溶劑經移除和乾燥,並視所須施壓(即,負極混合物糊施用程序),可製備包括負極混合物層在負極電流收集器上的負極片(即,負極製程)。 [0028]之後,將描述電極體製程(S30)。此程序中,在以上正極製程(S20)中製備的正極50和另外製備的負極60與介於其間的隔離物70層壓並捲繞以製備捲繞的電極體20(參照圖1)。作為安插於正和負極片50和60之間的隔離物70,可以使用使正極混合物層54與負極混合物層64隔絕且對於非水性電解質液具有阻滯功能和阻隔功能的任何材料。較佳的例子包括樹脂(如,聚乙烯(PE)、聚丙烯(PP)、聚酯、纖維素、和聚醯胺)製的多孔樹脂片(膜)。 [0029]之後,將描述電池組裝品建構程序(S40)。此程序中,製備之捲繞的電極體20納入矩形電池殼(未示)中,且用於外部連接的正極端和負極端配置於以電力連接至捲繞的電極體20的正極50(未形成配件52a的正極混合物層)和負極60(未形成配件62a的負極混合物層)之配件(基本上,蓋)中。同時,所欲的非水性電解質液注入殼中。之後,當電池殼藉方法(如,焊接)密封時,建構根據本具體實施例之電池組裝品。所用的非水性電解質液可以與相關技術中之此類型的電池所使用者相同且無特別限制。例如,含有元素氟的鋰鹽(載鹽)的較佳例子包括LiPF6
和LiBF4
。此外,非水性溶劑(即,有機溶劑)的較佳例子包括環狀碳酸酯(如,碳酸伸乙酯(EC)和碳酸伸丙酯(PC))、鏈碳酸酯溶劑(如,碳酸二甲酯(DMC)和碳酸甲酯乙酯(EMC))、和酯溶劑(如,丙酸乙酯(EP))。當鋰鹽以約0.1 mol/L至5 mol/L的濃度含於此非水性溶劑中時,可製備用於鋰離子二次電池的非水性電解質液。在非水性電解質液中,用以實現各式各樣的目的之各式各樣的添加劑,例如,添加劑(如,氣體生成劑、成膜劑、分散劑、稠化劑)可加至非水性電解質液。例如,氟磷酸鹽(如,二氟磷酸鋰(LiPO2
F2
))、草酸錯合物(如,雙草酸硼酸鋰(LiBOB))、碳酸伸乙烯酯等為適當的添加劑,其有助於改良電池的性能。此外,可以使用過度充電抑制劑,如,環己基苯和聯苯。 [0030]之後,在電池組裝品(其中,已供應非水性電解質液且電極體已納入其中的殼經密封)上進行初步充電程序(S50)。類似於相關技術的鋰離子二次電池,在用於外部連接的正極端和負極端之間連接外部電源供應器,且此電池組裝品於常溫(基本上,約25℃)初步充電直到介於正和負極端之間的電位達到預定電位。例如,作為初步充電,可以進行恆定電流和恆定電位充電(CC-CV充電),其中開始充電時,充電於約0.1C至10C的恆定電流進行直到正極端和負極端之間的電位達到預定電位(例如,4.3V至4.8V),且之後於恆定電位充電直到充電狀態(SOC)成為約60%至100%。或者,開始充電時,可以以1/3C或更低(基本上,1/20C至1/3C)的充電速率充電直到至少SOC達到20%,之後可以約0.1C至10C的恆定電流充電直到正極端和負極端之間的電位達到預定電位,且可於恆定電位進行額外的充電直到SOC變成約60%至100%。此外,在初步充電程序(S50)終了之後,作為額外的調節處理,可於實質上與恆定電流充電期間內相同的充電速率進行放電處理,及之後,可以於實質上相同電流值的速率數度進行充電和放電循環。或者,可以以不同於充電和放電循環的充電和放電速率數度進行充電和放電循環。 [0031]之後,進行老化處理時,可提供能夠展現有利的性能之鋰離子二次電池100。此老化處理藉由於高溫老化進行,其中,經初步充電的電池100維持於35℃或更高的溫度範圍達6小時或更長時間(較佳地,10小時或更長時間,例如,20小時或更長時間)。藉此,可提高在初步充電期間內形成於負極表面上的固態電解質中間相(SEI)塗膜的安定性並降低內部電阻。此外,能夠改良鋰離子二次電池於高溫儲存的耐久性。老化溫度較佳地約35℃至85℃(更佳為40℃至80℃,且最佳為50℃至70℃)。老化溫度低於此範圍時,降低初始內部電阻的效果不足。老化溫度高於此範圍時,非水性溶劑或鋰鹽會分解,電解質液會受損,且內部電阻會提高。未特別限制老化時間的上限。但是,當上限超過約50小時時,初始內部電阻顯著逐漸降低,且電阻值不太會改變。因此,考慮降低成本,老化時間較佳為約6小時至50小時(更佳為10小時至40小時,例如,20小時至30小時)。 [0032]以下將描述關於本發明的試驗例。但是,不欲將本發明限於此等特定實例。 [0033] <試驗例1> 製備Li5
FeO4
粉末。此處,Li2
O和α-Fe2
O3
以適當的化學計量比混合以製備混合的粉末材料且於高溫(例如,800℃至900℃)加熱達預定時間(例如,30分鐘至60分鐘)並反應,合成得到Li5
FeO4
。另一方面,製備LiNi0.5
Mn1.5
O4
,其為5 V-等級尖晶石結構鋰鎳錳複合氧化物作為正極活性材料。除了正極活性材料以外,乙炔黑(AB)作為導電性添加劑、聚丙烯酸(PAA:高度交聯的吸水性樹脂粒子)作為黏合劑(黏合劑)、和磷酸鋰(LPO)作為添加劑,其以LiNi0.5
Mn1.5
O4
:AB:PAA:LPO=90:5:2.2:2.8的質量比製備。 [0034]此外,以糊的固體總含量100重量%(100質量份)計,製備的Li5
FeO4
粉末以0.2重量%(0.2質量份)、0.3重量%(0.3質量份)、0.6重量%(0.6質量份)、0.8重量%(0.8質量份)、1.5重量%(1.5質量份)、2.0重量%(2.0質量份)、和 2.2重量%(2.2質量份)的添加量添加且共製備7種類型之含有Li5
FeO4
粉末和不同組成比例的水性正極混合物糊。特定言之,根據圖4所示的流程,混入材料並攪拌,混入適當量的去離子水,使得固體比率(NV)為70重量%或更高,並藉此製備水性正極混合物糊。即,首先,將 LiNi0.5
Mn1.5
O4
、乙炔黑(AB)、和Li5
FeO4
混合並攪拌約5分鐘。已有適當量的稠化劑(CMC)事先混入其中的去離子水加至經混合和攪拌的材料中,使得最終的固體比例(NV)為70%或更高,並使用攪拌棒(如,市售的行星式分散混合機)於4000 rpm 30分鐘進行分散處理。之後,添加聚丙烯酸,使用攪拌棒以人工攪拌此混合物約5分鐘,製得共7種類型之含有Li5
FeO4
粉末和不同組成比例的水性正極混合物糊。此處,在糊的製程中,適當地添加小量的磷酸,且糊的pH維持在中性範圍內(7至11)。 [0035]之後,所有製得的正極混合物糊施用至鋁箔(正極電流收集器)表面,藉滾壓加工形成密度已經調整至預定值的正極混合物層,其在大氣壓中於140℃乾燥30秒,且對應於製備的正極混合物糊,共製得共7種類型的正極片。 [0036]另一方面,以天然石墨為基礎的碳材料(C)作為負極活性材料、SBR作為黏合劑、和CMC作為稠化劑,以C:SBR:CMC=98:1:1的質量比稱得,適當量的去離子水混入,使得固體比例(NV)為70重量%,並藉此製備水性負極混合物糊。之後,製備的負極混合物糊施用至銅箔(負極電流收集器)表面,藉滾壓加工形成密度已經調整至預定值的負極混合物層,其在大氣壓中於140℃乾燥30秒,並藉此製備根據本試驗例的負極片。此外,作為鋰鹽的LiPF6
以1 mol/L的濃度溶於含有碳酸單氟伸乙酯(FEC)作為環狀碳酸酯和碳酸甲基-2,2,2-三氟乙酯(MTFEC)作為鏈碳酸酯(體積比為50:50)的混合溶劑中,且此經攪拌和混合以製備非水性電解質液。 [0037]所有製備的正極片、和負極片與介於其間的隔離物經層疊和捲繞以製備捲繞的電極體。使用具有聚乙烯(PE)∕聚丙烯(PP)∕聚乙烯(PE)之三層結構的多孔膜作為隔離物。之後,電極體和非水性電解質液納入層壓的電池殼中並於之後密封以建構出共7種類型之根據本試驗例的鋰離子二次電池組裝品。之後,所建構的試驗鋰離子二次電池組裝品在25℃的溫度環境下以0.3C的速率在介於0V和4.75V之間充電和放電,並進行初步充電程序。在初步充電程序之後,SOC狀態為100%的試驗電池納入60℃的恆熱槽中,並進行20小時的高溫老化。 [0038]完成高溫老化之後,試驗電池回到25℃的溫度環境,SOC調整至40%,之後測定AC阻抗。自所得阻抗的Nyquist圖讀取半圓的直徑並設定為反應電阻(Ω)。此處,用於AC阻抗的測定條件,施用的AC電位是5 mV而頻率範圍是0.001 Hz至100,000 Hz。之後,將使用含有添加量為0.2重量%(0.2質量份)的Li5
FeO4
的水性正極混合物糊所建構的電池的反應電阻值設定為參考值(1),計算使用含有預定比例的Li5
FeO4
之水性正極混合物糊所建構的電池所得到的反應電阻值相對於參考值之相對值(相對比)作為反應電阻比。其結果示於表1。 [表1]
[0044][0044]
100‧‧‧鋰離子二次電池100‧‧‧lithium ion secondary battery
20‧‧‧扁平的電極體20‧‧‧ flat electrode body
30‧‧‧電池殼30‧‧‧ Battery Case
32‧‧‧殼主體32‧‧‧shell body
34‧‧‧蓋34‧‧‧ cover
36‧‧‧排氣閥36‧‧‧ exhaust valve
42‧‧‧正極端42‧‧‧ positive extreme
42a‧‧‧正極端42a‧‧‧Positive Extreme
44‧‧‧負極端44‧‧‧ Negative terminal
44a‧‧‧負極端44a‧‧‧ Negative terminal
50‧‧‧拉長的正極50‧‧‧ elongated positive electrode
52‧‧‧拉長的正極電流收集器52‧‧‧ elongated positive current collector
52a‧‧‧拉長的正極電流收集器52a‧‧‧ elongated positive current collector
54‧‧‧正極混合物層54‧‧‧Positive electrode mixture layer
60‧‧‧拉長的負極60‧‧‧ elongated negative electrode
62‧‧‧拉長的負極電流收集器62‧‧‧ elongated negative current collector
62a‧‧‧拉長的負極電流收集器62a‧‧‧ elongated negative current collector
64‧‧‧負極混合物層64‧‧‧ Negative electrode mixture layer
70‧‧‧拉長的隔離物70‧‧‧ elongated partition
S10‧‧‧製備正極混合物糊的程序S10‧‧‧ Procedure for preparing positive electrode mixture paste
S20‧‧‧製備正極的程序S20‧‧‧Procedure for preparing positive electrode
S30‧‧‧製備電極體的程序S30‧‧‧ Procedure for preparing electrode body
S40‧‧‧建構電池組裝品的程序S40‧‧‧Procedure for building battery assembly
S50‧‧‧初步充電程序S50‧‧‧Preliminary charging procedure
[0016]以下將參照附圖描述本發明之例示具體實施例的特點、優點、及技術和工業意義,附圖中,類似的數字代表類似的元件,且其中: 圖1是出示根據具體實施例之鋰離子二次電池的構形之縱向截面示意圖; 圖2是出示根據具體實施例之鋰離子二次電池中所含括的電池體之構形的示意圖; 圖3是用於描述根據具體實施例製造鋰離子二次電池之程序的一般流程圖;和 圖4是用於描述根據具體實施例製造水性正極混合物糊之程序的一般流程圖。[0016] The features, advantages, and technical and industrial significance of the exemplified specific embodiments of the present invention will be described below with reference to the drawings. In the drawings, similar numbers represent similar elements, and among them: FIG. A schematic longitudinal sectional view of the configuration of a lithium-ion secondary battery; FIG. 2 is a schematic view showing the configuration of a battery body included in the lithium-ion secondary battery according to a specific embodiment; FIG. 3 is a diagram for describing a specific implementation A general flowchart of a procedure for manufacturing a lithium ion secondary battery is shown; and FIG. 4 is a general flowchart for describing a procedure of manufacturing an aqueous positive electrode mixture paste according to a specific embodiment.
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EP3960710A4 (en) * | 2019-04-26 | 2022-07-06 | Panasonic Intellectual Property Management Co., Ltd. | Positive electrode active material for secondary battery, and secondary battery |
CN110783532A (en) * | 2019-11-11 | 2020-02-11 | 天科新能源有限责任公司 | Preparation method of positive pole piece for lithium ion battery |
KR20210060825A (en) * | 2019-11-19 | 2021-05-27 | 주식회사 엘지에너지솔루션 | Methods of activation for secondary battery |
JP7240615B2 (en) * | 2020-02-17 | 2023-03-16 | トヨタ自動車株式会社 | Negative electrode for lithium ion secondary battery and manufacturing method thereof |
JP7232801B2 (en) | 2020-10-15 | 2023-03-03 | プライムプラネットエナジー&ソリューションズ株式会社 | Manufacturing method of lithium ion battery |
KR20230064749A (en) * | 2021-11-04 | 2023-05-11 | 주식회사 엘지에너지솔루션 | Fomation method for lithium secondary battery |
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